CN104795564A - Cathode material, electrode piece, secondary cell and application of aqueous-solution secondary cell - Google Patents
Cathode material, electrode piece, secondary cell and application of aqueous-solution secondary cell Download PDFInfo
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- CN104795564A CN104795564A CN201410490257.XA CN201410490257A CN104795564A CN 104795564 A CN104795564 A CN 104795564A CN 201410490257 A CN201410490257 A CN 201410490257A CN 104795564 A CN104795564 A CN 104795564A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a cathode material, an electrode piece, a secondary cell and an application of an aqueous-solution secondary cell. The cathode material is fluoridized phosphate, which has the chemical general formula of Na<2+beta>Fe<i>Mn<j>M<k>PO<4>F, wherein M is one or more elements selected from Li, Ni, Mg, Cu, Zn, Al, V, Co, Cr, Nb, Mo, and Ti; 0<=i<=1; 0<=j<=1; 0<=k<0.5; and -0.2<=beta<=0.1. The cathode material comprises two structures, wherein the first space group of the structures is Pbcn, and the cell parameters are that a=5.22+x, b=13.854+y, and c=11.7792+z; the second first group of the structures is P21/n, and the cell parameters are that a=13.68+x, b=5.3+y, and c=13.82+z; and -0.1<=x<=0.1, -0.1<=y<=0.1, and -0.1<=z<=0.1.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of positive electrode of Aqueous solution secondary battery, pole piece, secondary cell and purposes.
Background technology
Along with the minimizing of the non-renewable energy resources such as oil, coal and the aggravation of environmental pollution, development clean energy resource becomes global problem.Development wind energy, solar energy and energy-storage battery etc. supporting with it become the key solving this problem.Existing electrochemical storage device mainly contains lead-acid battery, nickel-zinc battery, nickel-hydrogen battery, flow battery and lithium ion battery etc.Wherein lithium rechargeable battery majority adopts Lithium-ion embeding compound as positive and negative pole material, using the organic solvent of drying as electrolyte.The deintercalation back and forth between both positive and negative polarity active material that lithium ion is reversible, and the structure of conversion materials can not be broken.Lithium ion battery due to operating voltage high (3.6V), be cadmium-nickel, three times of nickel-hydrogen battery; Volume is little, less than nickel-hydrogen battery by 30%; Quality is light, lighter than nickel-hydrogen battery by 50%; Specific energy high (200Wh/kg) is 2-3 times of cadmium nickel battery; Memory-less effect, pollution-free, self discharge is little, have extended cycle life, and becomes to generally acknowledge and promise to be the electrokinetic cell of electric automobile and the energy-storage battery of regenerative resource most.But, because lithium resource is limited and extraction cost is high, lithium ion battery cost is raised, the low cost demand of large-scale application cannot be met; And organic system lithium ion battery due to an organic solvent with the lithium salts of costliness as electrolyte, bring a lot of uncertain safety problem.
Extensive energy-storage battery aqueous electrolyte replaces organic electrolyte to be considered to one of the most promising method.Although the stable electrochemical window of aqueous electrolyte is narrow, output voltage is lower, and water solution system ionic conductivity two orders of magnitude higher than organic system, therefore may be used for high rate charge-discharge.And the assembling of aqueous solution battery, without the need for the such exacting terms of body system, so just greatly reduces the cost of water system battery.Same employing inlaid scheme is as the positive and negative pole material of aqueous solution battery, with the electrolyte of the aqueous solution as this battery, utilize the operation principle that lithium rechargeable battery is similar, water solution chargeable discharge battery also can accomplish low cost, coefficient of safety is high, long service life, non-environmental-pollution, power advantages of higher, becomes the energy storage device of new generation with development and application potentiality.
Due to the restriction of stabilized aqueous solution electrochemical window, the oxidation-reduction potential of the alternative positive electrode of this system will lower than the oxygenous current potential of water decomposition, and negative material needs selective redox current potential to produce the current potential of hydrogen higher than water decomposition.The current potential that hydrogen and oxygen are separated out in water decomposition has close relationship with the pH of the aqueous solution again.Therefore determine a kind of Aqueous solution secondary battery that can be applicable to, the electrode material of excellent performance is problem demanding prompt solution.
Summary of the invention
The invention provides a kind of positive electrode of Aqueous solution secondary battery, pole piece, secondary cell and purposes, this material is fluorinated phosphate salt material, with low cost, safety non-toxic, and de-sodium current potential is within stabilized aqueous solution electrochemical window; Higher, the first all coulombic efficiencies of the Aqueous solution secondary battery capacity prepared with it are high, may be used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
First aspect, embodiments provides a kind of positive electrode of Aqueous solution secondary battery, and described material is fluorinated phosphate salt, and chemical general formula is: Na
2+ βfe
imn
jm
kpO
4f;
Wherein, M is element transition metal position being carried out to doped and substituted, comprises Li, one or more in Ni, Mg, Cu, Zn, Al, V, Co, Cr, Nb, Mo, Ti; 0≤i≤1; 0≤j≤1; 0≤k<0.5;-0.2≤β≤0.1;
Described positive electrode comprises two kinds of structures, and the first is orthohormbic structure, and space group is Pbcn, cell parameter a=5.22+x, b=13.854+y, c=11.7792+z; The second space group is P2
1/ n, cell parameter is a=13.68+x, b=5.3+y, c=13.82+z; Wherein ,-0.1≤x≤0.1 ,-0.1≤y≤0.1 ,-0.1≤z≤0.1.
Second aspect, embodiments provides a kind of anode pole piece of Aqueous solution secondary battery, comprising:
Suppress after collector, coating or mixing electronic conductance material on described collector, binding agent, as above-mentioned positive electrode according to claim 1 and/or additive;
Wherein, described additive is separated out in order to stop oxygen or hydrogen.
Preferably, described conductive additive comprises: one or more in graphite, carbon black, acetylene black, metal dust, SuperP, carbon nano-tube, Graphene.
Preferably, described binding agent comprises:
Kynoar PVDF, one or more in polytetrafluoroethylene PTFE, sodium alginate, sodium carboxymethylcellulose CMC or polyacrylic acid PAA.
Preferably, described collector comprises: titanium net or stainless (steel) wire.
The third aspect, embodiments provides a kind of Aqueous solution secondary battery, comprises the anode pole piece described in above-mentioned second aspect, barrier film, cathode pole piece and electrolyte solution.
Preferably, the negative material that described cathode pole piece is used comprises: NaTi
2(PO
4)
3, Na
2feTi (PO
4)
3, one or more in active carbon.
Preferably, the pH value of described electrolyte solution is between 1-14, and concentration of electrolyte solutions is 0.1mol/L-15mol/L;
Described electrolyte solution comprises: one or more in sodium sulphate, sodium nitrate, sodium halide, sodium acetate, NaOH, sodium phosphate, sodium oxalate.
Preferred further, also comprise additive in described electrolyte solution, in order to improve liberation of hydrogen or oxygen evolution potential;
Described additive comprises: the water-soluble salt containing Pb, Cd or Zn.
Fourth aspect, embodiments provide the purposes of the Aqueous solution secondary battery described in a kind of above-mentioned 3rd, described Aqueous solution secondary battery is used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
The positive electrode of the Aqueous solution secondary battery that the embodiment of the present invention provides is fluorinated phosphate salt material, with low cost, safety non-toxic, and de-sodium current potential is within stabilized aqueous solution electrochemical window; Higher, the first all coulombic efficiencies of the Aqueous solution secondary battery capacity prepared with it are high, have extended cycle life, and may be used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
Accompanying drawing explanation
Below by drawings and Examples, the technical scheme of the embodiment of the present invention is described in further detail.
X-ray diffraction (XRD) collection of illustrative plates of a kind of fluorinated phosphate salt material that Fig. 1 provides for the embodiment of the present invention 2;
The SEM figure of a kind of fluorinated phosphate salt material that Fig. 2 provides for the embodiment of the present invention 2;
The typical cyclic voltammogram of the half-cell of a kind of fluorinated phosphate salt material that Fig. 3 provides for the embodiment of the present invention 2;
A kind of fluorinated phosphate salt material that Fig. 4 provides for the embodiment of the present invention 2 is to NaTi
2(PO
4)
3full battery charging and discharging figure;
A kind of fluorinated phosphate salt material that Fig. 5 provides for the embodiment of the present invention 3 is to NaTi
2(PO
4)
3full battery charging and discharging figure;
A kind of fluorinated phosphate salt material that Fig. 6 provides for the embodiment of the present invention 3 is to NaTi
2(PO
4)
3full battery charging and discharging multiplying power figure;
A kind of fluorinated phosphate salt material that Fig. 7 provides for the embodiment of the present invention 4 is to Na
2feTi
2(PO
4)
3full battery charging and discharging figure;
A kind of fluorinated phosphate salt material that Fig. 8 provides for the embodiment of the present invention 6 in organic electrolyte system to the typical charge and discharge electrograph of sodium metal battery;
The XRD collection of illustrative plates of the another kind of fluorinated phosphate salt material that Fig. 9 provides for the embodiment of the present invention 9;
The SEM figure of the another kind of fluorinated phosphate salt material that Figure 10 provides for the embodiment of the present invention 9.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not intended to limit the scope of the invention.
Embodiment 1
The embodiment of the present invention 1 provides a kind of positive electrode of Aqueous solution secondary battery, and be fluorinated phosphate salt, chemical general formula is: Na
2+ βfe
imn
jm
kpO
4f.
Wherein, M is element transition metal position being carried out to doped and substituted, comprises Li, one or more in Ni, Mg, Cu, Zn, Al, V, Co, Cr, Nb, Mo, Ti; 0≤i≤1; 0≤j≤1; 0≤k<0.5;-0.2≤β≤0.1; .Wherein this positive electrode can have two kinds of structures: a kind of is orthohormbic structure, and as shown in Figure 2, space group is Pbcn, cell parameter (unit is dust) a=5.22+x, b=13.854+y, c=11.7792+z; Wherein ,-0.1≤x≤0.1 ,-0.1≤y≤0.1 ,-0.1≤z≤0.1; As shown in Figure 10, space group is P2 to another kind of structure
1/ n, cell parameter (unit is dust) is a=13.68+x, b=5.3+y, c=13.82+z; Wherein ,-0.1≤x≤0.1 ,-0.1≤y≤0.1 ,-0.1≤z≤0.1.
The positive electrode of the Aqueous solution secondary battery of the fluorinated phosphate salt that the embodiment of the present invention provides, safety non-toxic, de-sodium current potential, within stabilized aqueous solution electrochemical window, can be applied in aqueous solution sodium ion secondary battery or aqueous solution lithium rechargeable battery as positive electrode active materials.
Method and the battery behavior of the positive electrode applicability of secondary batteries of the Aqueous solution secondary battery of fluorinated phosphate salt the above embodiment of the present invention provided are described with multiple instantiation below.
Embodiment 2
The present embodiment adopts Solid phase synthesis Na
2fePO
4f, its XRD collection of illustrative plates refers to Fig. 1, and granule-morphology in detail as shown in Figure 2.
Anode pole piece composition is according to Na
2fePO
4f: carbon black: the mass ratio Homogeneous phase mixing of Kynoar (PVDF)=80:15:5, suppresses on stainless (steel) wire collector, as positive electrode after oven dry.Wherein, stainless (steel) wire preferably adopts 306 type stainless (steel) wires.Platinized platinum is adopted to electrode, reference electrode silver silver chloride electrode.With 1.5mol/L aqueous sodium persulfate solution as electrolyte, be assembled into three-electrode battery.
Under sweep speed is 5mV/s speed, cyclic voltammetry scan test is carried out to the battery prepared.Obtain cyclic voltammogram as shown in Figure 3.Known according to test, the invertibity of electrode reaction is good.Fig. 4 shows this fluorinated phosphate salt material to NaTi
2(PO
4)
3full battery charging and discharging long circulating figure, this circulating battery 700 weeks, reversible specific capacity is initial specific capacities 66%.
Embodiment 3
The present embodiment adopts Solid phase synthesis Na
2fePO
4f is identical with above-described embodiment 2.
Anode pole piece composition is according to Na
2fePO
4the mass ratio Homogeneous phase mixing of F: carbon black: PVDF=70:25:5, suppresses on stainless (steel) wire collector, as positive electrode after oven dry.Negative pole adopts NaTi
2(PO
4)
3, negative pole is according to NaTi
2(PO
4)
3: Super P:PVDF=75:20:5 Homogeneous phase mixing, on coating stainless (steel) wire collector, is pressed into negative electrode after oven dry.Adopt the nonwoven fabrics of commercial Ni-MH battery as barrier film, with 2mol/L aqueous sodium persulfate solution as electrolyte, be assembled into R2032 button cell.
Battery is tested, test voltage scope be charging and discharging curve under 0V-1.4V, 1C multiplying power as shown in Figure 5.Battery first all specific discharge capacities under 1C multiplying power are 100mAh/g.Charging and discharging curve figure as shown in Figure 6 again, battery first all specific discharge capacities under 2C multiplying power are that under 95mAh/g, 10C multiplying power, first Zhou Fang electricity is 60mAh/g.
Embodiment 4
The present embodiment adopts Solid phase synthesis Na
2fePO
4f is identical with above-described embodiment 2.
Anode pole piece composition is according to Na
2fePO
4the mass ratio Homogeneous phase mixing of F: acetylene black: PVDF=75:20:5, suppresses on titanium net collector, as positive electrode after oven dry.Negative pole adopts Na
2feTi (PO
4)
3, negative pole is according to Na
2feTi (PO
4)
3: the mass ratio Homogeneous phase mixing of Super P:PVDF=75:20:5, is coated on titanium net collector, is pressed into negative electrode after oven dry.Adopt the nonwoven fabrics of commercial Ni-MH battery as barrier film, with 1mol/L sodium nitrate aqueous solution as electrolyte, be assembled into R2032 button cell.
Test battery, test voltage scope is 0V-1.4V, battery under the multiplying power of 1C charging and discharging curve as shown in Figure 7, first all specific discharge capacities are 53mAh/g.
Embodiment 5
The present embodiment adopts Solid phase synthesis Na
1.95fe
0.95al
0.05pO
4f.
Anode pole piece composition is according to Na
1.95fe
0.95al
0.05pO
4the mass ratio Homogeneous phase mixing of F: carbon black: PVDF=80:10:10, suppresses on stainless (steel) wire collector, as positive electrode after oven dry.Active carbon is adopted, according to active carbon to electrode: PTFE=95:5 ratio uniform mixes, and is compressed on as negative electrode on stainless steel collector, reference electrode silver silver chloride electrode.With 10mol/L sodium nitrate aqueous solution as electrolyte, be assembled into three-electrode battery.
Embodiment 6
The present embodiment adopts Solid phase synthesis Na
2fe
0.95cu
0.05pO
4f.
Anode pole piece composition is according to Na
2fe
0.95cu
0.05pO
4the mass ratio Homogeneous phase mixing of F: carbon black: PVDF=80:10:10, suppresses on stainless (steel) wire collector, as positive electrode after oven dry.Active carbon is adopted, according to active carbon to electrode: the mixing of PTFE=95:5 ratio uniform is pressed on stainless steel collector, as negative electrode, reference electrode silver silver chloride electrode.With 5mol/L sodium nitrate aqueous solution as electrolyte, be assembled into three-electrode battery.
Test sodium half-cell in organic electrolyte battery, test voltage scope is 2V-4V, and as shown in Figure 8, first all specific discharge capacities are 85mAh/g to the charge-discharge test curve of battery.
Embodiment 7
The present embodiment adopts Solid phase synthesis Na
2fe
0.8mn
0.2pO
4f.
Anode pole piece composition is according to Na
2fe
0.
8mn
0.
2pO
4the mass ratio Homogeneous phase mixing of F: carbon black: PVDF=80:15:5, suppresses on stainless (steel) wire collector, as positive electrode after oven dry.Negative pole adopts NaTi
2(PO
4)
3, according to NaTi
2(PO
4)
3: the mixing of Super P:PTFE=80:15:5 ratio uniform is compressed on stainless steel collector, as negative electrode; Make barrier film with the glass fibre that Whatman produces, with 2mol/L aqueous sodium acetate solution as electrolyte, be assembled into the button cell of R2032 type.
Embodiment 8
The present embodiment adopts Solid phase synthesis Na
2.05fe
0.95na
0.05pO
4f.
Anode pole piece composition is according to Na
2.05fe
0.95na
0.05pO
4f: carbon black: the mass ratio Homogeneous phase mixing of polytetrafluoroethylene (PTFE)=80:15:5, suppresses on stainless (steel) wire collector, as positive electrode after oven dry.Negative pole adopts Na
2feTi (PO
4)
3, according to Na
2feTi (PO
4)
3: the mixing of Super P:PTFE=80:15:5 ratio uniform is suppressed on stainless steel collector, as negative electrode; Make barrier film with the glass fibre that Whatman produces, with 5mol/L aqueous sodium acetate solution as electrolyte, be assembled into the button cell of R2032 type.
Embodiment 9
The present embodiment adopts Solid phase synthesis Na
2.05fe
0.95na
0.05pO
4as shown in Figure 9, granule-morphology in detail as shown in Figure 10 for F, its XRD.
Anode pole piece composition is according to Na
2.05fe
0.95na
0.05pO
4the mass ratio Homogeneous phase mixing of F: carbon black: PTFE=80:15:5, suppresses on stainless (steel) wire collector, as positive electrode after oven dry.Negative pole adopts NaTi
2(PO
4)
3, according to NaTi
2(PO
4)
3: Super P:PTFE=80:15:5 ratio uniform mixes, and is compressed on stainless steel collector, forms negative electrode; Make barrier film with nonwoven fabrics, with 1mol/L aqueous sodium acetate solution as electrolyte, be assembled into the button cell of R2032 type.
Embodiment 10
The present embodiment adopts Solid phase synthesis Na
2fe
0.95ni
0.05pO
4f.
Anode pole piece composition is according to Na
2fe
0.95ni
0.05pO
4the equal Homogeneous phase mixing of mass ratio of F: carbon black: PTFE=70:25:5, suppresses on titanium net collector, as positive electrode after oven dry.Negative pole adopts active carbon, according to active carbon: PTFE=95:5 ratio uniform mixes, and is compressed on stainless (steel) wire collector, forms negative electrode after oven dry.Adopt the nonwoven fabrics of commercial Ni-MH battery as barrier film, with 3mol/L sodium nitrate aqueous solution as electrolyte, be assembled into R2032 button cell.
Embodiment 11
The present embodiment adopts Solid phase synthesis Na
2fe
0.95mg
0.05pO
4f.
Anode pole piece composition is according to Na
2fe
0.95mg
0.05pO
4the equal Homogeneous phase mixing of mass ratio of F: carbon black: PTFE=70:25:5, suppresses on titanium net collector, as positive electrode after oven dry.Negative pole adopts NaTi
2(PO
4)
3, according to NaTi
2(PO
4)
3: Super P:PVDF=75:20:5 ratio uniform mixes, and is coated on stainless (steel) wire collector, forms negative electrode after oven dry.Adopt the nonwoven fabrics of commercial Ni-MH battery as barrier film, with 0.8mol/L aqueous sodium persulfate solution as electrolyte, be assembled into R2032 button cell.
Although above-described embodiment 2-11 is described for the positive electrode applied solid phase method and prepare Aqueous solution secondary battery of the present invention, and be applied to method and the battery behavior of secondary cell, but not limiting the present invention can only adopt solid phase method to carry out the preparation of positive electrode, those skilled in the art easily expect, other method also can be adopted as sol-gel process, spray drying process, hydro thermal method etc. obtain positive electrode of the present invention.
State on the invention in embodiment, the binding agent used in anode pole piece is only for PVDF and PTFE, electronic conductive material is also only illustrated for carbon black, acetylene black, in actual applications, is not limited to this several material provided in above-described embodiment.Electronic conductance material can adopt graphite, carbon black, acetylene black, metal dust, Super P or other electric conducting material; Binding agent can adopt PVDF, PTFE, CMC, sodium alginate, PAA etc.; The additive stoping oxygen or hydrogen to be separated out can be added in addition.Anode pole piece prepares titanium net, the stainless (steel) wire that collector used is also not limited in above-described embodiment, can also comprise titanium foil, nickel screen etc.
In addition, positive electrode can also be carry out in-situ one-step synthesis bag carbon or with chemical meteorology deposition, and the predecessor containing carbon such as ionic liquid, sucrose, glucose carries out cracking and obtains the coated material of carbon in argon gas atmosphere.Above-mentioned material mixing can make the slurry of certain viscosity, this slurry is coated in or is suppressed on a current collector, can obtain anode pole piece of the present invention.
Electrolyte solution selected in Aqueous solution secondary battery of the present invention, except the sodium sulphate exemplified in above-described embodiment, sodium acetate, sodium nitrate, can also comprise sodium halide, NaOH, sodium phosphate, sodium oxalate etc.The pH of solution is 1-14, can regulate the pH value of electrolyte solution especially by the aqueous solution such as interpolation nitric acid, sulfuric acid, phosphoric acid or NaOH, sodium acid carbonate, sodium carbonate; Wherein pH value is preferably 5-9.Concentration of electrolyte solutions scope, at 0.1mol/L-15mol/L, is wherein preferably 0.5mol/L-10mol/L.Can also add suitable additive in electrolyte to improve liberation of hydrogen or oxygen evolution potential, described additive more such as can contain water-soluble salt of Pb, Cd or Zn.
The positive electrode of the Aqueous solution secondary battery of the fluorinated phosphate salt that the embodiment of the present invention provides, with low cost, safety non-toxic, de-sodium current potential is within stabilized aqueous solution electrochemical window; Higher, the first all coulombic efficiencies of the Aqueous solution secondary battery capacity prepared with it are high, may be used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; the protection range be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a positive electrode for Aqueous solution secondary battery, is characterized in that, described material is fluorinated phosphate salt, and chemical general formula is: Na
2+ βfe
imn
jm
kpO
4f;
Wherein, M is element transition metal position being carried out to doped and substituted, comprises Li, one or more in Ni, Mg, Cu, Zn, Al, V, Co, Cr, Nb, Mo, Ti; 0≤i≤1; 0≤j≤1; 0≤k<0.5;-0.2≤β≤0.1;
Described positive electrode comprises two kinds of structures, and the first is orthohormbic structure, and space group is Pbcn, cell parameter a=5.22+x, b=13.854+y, c=11.7792+z; The second space group is P2
1/ n, cell parameter is a=13.68+x, b=5.3+y, c=13.82+z; Wherein ,-0.1≤x≤0.1 ,-0.1≤y≤0.1 ,-0.1≤z≤0.1.
2. an anode pole piece for Aqueous solution secondary battery, is characterized in that, described anode pole piece comprises:
Suppress after collector, coating or mixing electronic conductance material on described collector, binding agent, as above-mentioned positive electrode according to claim 1 and/or additive;
Wherein, described additive is separated out in order to stop oxygen or hydrogen.
3. anode pole piece according to claim 2, is characterized in that, described conductive additive comprises: one or more in graphite, carbon black, acetylene black, metal dust, Super P, carbon nano-tube, Graphene.
4. anode pole piece according to claim 2, is characterized in that, described binding agent comprises:
Kynoar PVDF, one or more in polytetrafluoroethylene PTFE, sodium alginate, sodium carboxymethylcellulose CMC or polyacrylic acid PAA.
5. anode pole piece according to claim 2, is characterized in that, described collector comprises: titanium net or stainless (steel) wire.
6. an Aqueous solution secondary battery, is characterized in that, described Aqueous solution secondary battery comprises: anode pole piece, barrier film, cathode pole piece and electrolyte solution described in the arbitrary claim of the claims 2-5.
7. Aqueous solution secondary battery according to claim 6, is characterized in that, described cathode pole piece negative material used comprises: NaTi
2(PO
4)
3, Na
2feTi (PO
4)
3, one or more in active carbon.
8. Aqueous solution secondary battery according to claim 6, is characterized in that, the pH value of described electrolyte solution is between 1-14, and concentration of electrolyte solutions is 0.1mol/L-15mol/L;
Described electrolyte solution comprises: one or more in sodium sulphate, sodium nitrate, sodium halide, sodium acetate, NaOH, sodium phosphate, sodium oxalate.
9. Aqueous solution secondary battery according to claim 8, is characterized in that, also comprises additive in described electrolyte solution, in order to improve liberation of hydrogen or oxygen evolution potential;
Described additive comprises: the water-soluble salt containing Pb, Cd or Zn.
10. the purposes of the Aqueous solution secondary battery as described in the claims 6-9, it is characterized in that, described Aqueous solution secondary battery is used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
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| CN106206063A (en) * | 2016-08-13 | 2016-12-07 | 代相臣 | Water system hybrid super capacitor and preparation method thereof |
| CN108698828A (en) * | 2015-12-21 | 2018-10-23 | 魁北克电力公司 | Olivine compounds, preparation method and the purposes in the cathode material of sodium-ion battery |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108698828A (en) * | 2015-12-21 | 2018-10-23 | 魁北克电力公司 | Olivine compounds, preparation method and the purposes in the cathode material of sodium-ion battery |
| US11569506B2 (en) | 2015-12-21 | 2023-01-31 | HYDRO-QUéBEC | Olivine-type compounds: method for their preparation and use in cathode materials for sodium-ion batteries |
| CN106206063A (en) * | 2016-08-13 | 2016-12-07 | 代相臣 | Water system hybrid super capacitor and preparation method thereof |
| CN109952679A (en) * | 2016-11-14 | 2019-06-28 | 株式会社东芝 | Nonaqueous electrolyte battery and battery pack |
| CN109952679B (en) * | 2016-11-14 | 2022-06-14 | 株式会社东芝 | Nonaqueous electrolyte battery and battery pack |
| CN108832099A (en) * | 2018-06-15 | 2018-11-16 | 中南大学 | A kind of richness sodium phase sodium-ion battery positive material and its preparation and application |
| CN114026716A (en) * | 2019-09-20 | 2022-02-08 | 株式会社Lg新能源 | Irreversible additive contained in positive electrode material for secondary battery, positive electrode material containing same, and secondary battery containing same |
| CN114026716B (en) * | 2019-09-20 | 2023-10-03 | 株式会社Lg新能源 | Positive electrode material comprising irreversible additive and secondary battery comprising positive electrode material |
| WO2023193372A1 (en) * | 2022-04-07 | 2023-10-12 | 深圳沃伦特新能源科技有限公司 | Binary-doped iron-based fluorophosphate sodium ion positive electrode material and preparation method therefor |
| CN116741975A (en) * | 2023-08-15 | 2023-09-12 | 北京理工大学 | Double-carbon-layer heterogeneous composite positive electrode material, preparation method thereof and sodium ion battery |
| CN116741975B (en) * | 2023-08-15 | 2023-12-01 | 北京理工大学 | Double-carbon-layer heterogeneous composite positive electrode material, preparation method thereof and sodium ion battery |
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